Antimicrobial compositions

ABSTRACT

This invention concerns antimicrobial compositions that are useful for industrial applications. More specifically, it concerns antimicrobial compositions that, by combining 3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and one or more of 1-[[(3-iodo-2-propynyl)oxy]methoxy]-4-methoxy benzene, 1-chloro-4-[[(3-iodo-2-propynyl)oxy]methoxy]benzene, Zinc 2-pyridine thiol-1-oxide, Copper 2-pyridine thiol-1-oxide, 2-pyridine thiol- 1 -oxide sodium salt, 2,2-dithio-bis(pyridine-1-oxide), 2-methylthio-4-t-butyl amino-6-cyclopropyl amino-s-triazine, 3-iodo-2-propynyl butylcarbamate (IPBC), 2-(n-octyl)-3(2H)-isothiazolone (OIT), 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone (DCOIT), 2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile (chlorothalonil), 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenyl-methanesulfenamide (dichlofluanid), or 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)-methanesulfenamide (tolylfluanid) have the synergistic effect of these compounds.

[0001] This invention concerns antimicrobial compositions that areuseful for industrial applications. More specifically, it concernsantimicrobial compositions that, by combining3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and one ormore of 1-[[(3-iodo-2-propynyl)oxy]methoxy]-4-methoxy benzene,1-chloro-4-[[(3-iodo-2-propynyl)oxy]methoxy]benzene, Zinc 2-pyridinethiol-1-oxide, Copper 2-pyridine thiol-1-oxide, 2-pyridine thiol-1-oxidesodium salt, 2,2-dithio-bis(pyridine-1-oxide), 2-methylthio-4-t-butylamino-6-cyclopropyl amino-s-triazine, 3-iodo-2-propynyl butylcarbamate(IPBC), 2-(n-octyl)-3(2H)-isothiazolone (OIT),4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone (DCOIT),2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile (chlorothalonil),1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenyl-methanesulfenamide(dichlofluanid), or1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)-methanesulfenamide(tolylfluanid) have the synergistic effect of these compounds.

[0002] Inorganic or organic compounds that contain mainly mercury, tin,copper, and other heavy metals (hereafter called “heavy-metalcompounds”) have been widely used as antimicrobial agents for industrialproducts and industrial raw materials. But the high toxicity of theseheavy-metal compounds poses the danger of adversely affecting the humanbody. In addition, heavy-metal compounds are not suitable for use asantimicrobial agents because of the fear that heavy-metal compounds maylead to environmental destruction.

[0003] The many non-metallic antimicrobial agents that have beendeveloped to solve such problems of heavy metal compounds (for example,organic iodine compounds, nitrile compounds, isothiazolone compounds,benzimidazole compounds, pyrithione compounds) have selectivity in theirantimicrobial spectrum. Thus even if these non-metallic antimicrobialagents are applied to industrial products or industrial raw materials,in particular organic materials (for example, fibre, paint, adhesives,etc.), micro-organisms on which these antimicrobial agents have littleor no effect will grow and propagate, thus allowing the occurrence ofcontamination of industrial products, etc. or a change in the quality(for example, degradation) of industrial raw materials. Thereforesatisfactory antimicrobial effect cannot be obtained by conventionalantimicrobial compositions.

[0004] Thus attempts have been made to expand the antimicrobial spectrumand increase the antimicrobial effect by combining two or moreantimicrobial agents. But usually either the effect of only one of theantimicrobial agents appears, or only an additive effect is obtained.

[0005] The purpose of this invention, which is intended to solve theabove problems, is to provide antimicrobial compositions that are highlysafe, are very effective, and have a wide antimicrobial spectrum.

[0006] As a result of diligent study to solve the above problems, theinventors of this invention found that an unexpected synergistic effectis obtained by combining with3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide one or moreof the following compounds (a)-(m):

[0007] (a) 1-[[(3-iodo-2-propynyl)oxy]methoxy]-4-methoxy benzene

[0008] (b) 1-chloro-4-[[(3-iodo-2-propynyl)oxy]methoxy]benzene

[0009] (c) Zinc 2-pyridine thiol-1-oxide

[0010] (d) Copper 2-pyridine thiol-1-oxide

[0011] (e) 2-pyridine thiol-1-oxide sodium salt

[0012] (f) 2,2-dithio-bis(pyridine-1-oxide)

[0013] (g) 2-methylthio-4-t-butyl amino-6-cyclopropyl amino-s-triazine(irgarol)

[0014] (h) 3-iodo-2-propynyl butylcarbamate (IPBC)

[0015] (i) 2-(n-octyl)-3(2H)-isothiazolone (OIT)

[0016] (j) 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone (DCOIT)

[0017] (k) 2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile(chlorothalonil)

[0018] (l)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenyl-methanesulfenamide(dichlofluanid)

[0019] (m)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)-methanesulfenamide(tolylfluanid).

[0020] That is, they arrived at the perfection of this invention havingdiscovered that by combining3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and theabove compounds (a)-(m), one obtains antimicrobial compositions that aremore effective, and have a wider antimicrobial spectrum, than if eachcompound is used singly.

[0021] This invention provides antimicrobial composition comprising3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and one ormore of the following compounds (a)-(m):

[0022] (a) 1-[[(3-iodo-2-propynyl)oxy]methoxy]-4-methoxy benzene

[0023] (b) 1-chloro-4-[[(3-iodo-2-propynyl)oxy]methoxy]benzene

[0024] (c) Zinc 2-pyridine thiol-1-oxide

[0025] (d) Copper 2-pyridine thiol-1-oxide

[0026] (e) 2-pyridine thiol-1-oxide sodium salt

[0027] (f) 2,2-dithio-bis(pyridine-1-oxide)

[0028] (g) 2-methylthio-4-t-butyl amino-6-cyclopropyl amino-s-triazine(irgarol)

[0029] (h) 3-iodo-2-propynyl butylcarbamate (IPBC)

[0030] (i) 2-(n-octyl)-3(2H)-isothiazolone (OIT)

[0031] (j) 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone (DCOIT)

[0032] (k) 2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile(chlorothalonil)

[0033] (l)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenyl-methanesulfenamide(dichlofluanid)

[0034] (m)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)-methanesulfenamide(tolylfluanid).

[0035] Preferably the weight ratio of above3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and abovecompounds (a)-(m) should be in the range 20:1 to 1:20. More preferably,the weight ratio of above3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and abovecompounds (a)-(m) should be in range 5:1 to 1:5.

[0036] The technical term “antimicrobial composition” used in thisspecification means a composition that has the effect of inhibiting thegrowth of bacteria, fungi, yeast, algae, etc. or killing thesemicro-organisms.

[0037] A. Composition of the Invention

[0038] A.1. Effective Components

[0039] The antimicrobial compositions of this invention comprise as itseffective components3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and one ormore of the following compounds (a)-(m):

[0040] (a) 1-[[(3-iodo-2-propynyl)oxy]methoxy]4-methoxy benzene

[0041] (b) 1-chloro-4-[[(3-iodo-2-propynyl)oxy]methoxy]benzene

[0042] (c) Zinc 2-pyridine thiol-1-oxide

[0043] (d) Copper 2-pyridine thiol-1-oxide

[0044] (e) 2-pyridine thiol-1-oxide sodium salt

[0045] (f) 2,2-dithio-bis(pyridine-1-oxide)

[0046] (g) 2-methylthio-4-t-butyl amino-6-cyclopropyl amino-s-triazine(irgarol)

[0047] (h) 3-iodo-2-propynyl butylcarbamate (IPBC)

[0048] (i) 2-(n-octyl)-3(2H)-isothiazolone (OIT)

[0049] (j) 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone (DCOIT)

[0050] (k) 2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile(chlorothalonil)

[0051] (1)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenyl-methanesulfenamide(dichlofluanid)

[0052] (m)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)-methanesulfenamide(tolylfluanid).

[0053] 3-Benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide canbe synthesized by, for example, the method described in JP-B2-2761441.

[0054] 1-[[(3-Iodo-2-propynyl)oxy]methoxy]-4-methoxy benzene can besynthesized by, for example, the method described in JP-B2-2852289.

[0055] 1-Chloro-4-[[(3-iodo-2-propynyl)oxy]methoxy]benzene can besynthesized by, for example, the method described in JP-B-47-24121.

[0056] Zinc 2-pyridine thiol-1-oxide can be synthesized by, for example,the method described in U.S. Pat. No. 3,583,999.

[0057] Copper 2-pyridine thiol-1-oxide can be synthesized by, forexample, the method described in JP-B2-3062825.

[0058] 2-Pyridine thiol-1-oxide sodium salt can be synthesized by, forexample, the method described in U.S. Pat. No. 4,396,766.

[0059] 2,2-Dithio-bis(pyridine-1-oxide) can be synthesized by, forexample, the method described in U.S. Pat. No. 3,892,760.

[0060] 2-Methylthio-4-t-butyl amino-6-cyclopropyl amino-s-triazine canbe synthesized by, for example, the method described in DE-A-1914014.

[0061] The proportion between3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m) in the antimicrobial compositions can be appropriatelyselected according to the types of target micro-organisms and theconditions under which above composition is to be used as anantimicrobial agent. Normally, the proportion between3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m) is, in weight ratio, in the range 20:1 to 1:20,preferably 5:1 to 1:5, and especially preferably 3:1 to 1:3.

[0062] The antimicrobial compositions of this invention can be used in aform that fits its purpose of use. For example, the antimicrobialcompositions of this invention may be simply a mixture of3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m), but preferably it can include, besides3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m), an appropriate solvent and dispersant or carrier orother component.

[0063] The total content of3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m) in the composition of this invention varies with theproduct form and purpose of use, etc., but usually it is 0.1% by weightto 95% by weight, and preferably 0.2% by weight to 60% by weight, of thetotal antimicrobial compositions that is obtained.

[0064] The amount of the antimicrobial compositions of this invention touse varies with the composition and the type and concentration of themicro-organisms on which it is to be used, but generally, if it is to beused on fibre, paint, adhesive, etc., a good effect is obtained at about1-10,000 mg/kg.

[0065] A.2. Solvents and Dispersants

[0066] If the system in which it is to be used is an industrial watersystem of any of various types, in consideration of the dissolvabilityand dispersibility of the effective components and other factors, it isdesirable to prepare a liquid formulation that includes a solvent anddispersant, as discussed below.

[0067] As the solvent that can be used in the antimicrobial compositionsof this invention, one may cite any solvent that does not adverselyaffect the active ingredients, for example, water, alcohols (forexample, methyl alcohol, ethyl alcohol, ethylene glycol, propyleneglycol, diethylene glycol, glycerin, etc.), ketones (for example,acetone, methyl ethyl ketone, etc.), ethers (for example, dioxane,tetrahydrofurane, cellosolve, diethylene glycol dimethyl ether, etc.),aliphatic hydrocarbons (for example, hexane, kerosene, etc.), aromatichydrocarbons (for example, benzene, toluene, xylene, solvent naphtha,methyl naphthalene, etc.), halogenated hydrocarbons (for example,chloroform, carbon tetrachloride, etc.), acid amides (for example,dimethyl formadide, etc.), esters (for example, methyl acetate ester,ethyl acetate ester, butyl acetate ester, fatty acid glycerin ester,etc.), and nitrols (for example, acetonitrile, etc.). These solvents maybe used either singly or in combination of two or more species.

[0068] As the dispersant that can be used in the antimicrobialcompositions of this invention, one may cite any dispersant that doesnot adversely affect the active ingredients, for example, a surfactant.As such surfactants, one may cite soaps, high-grade alcohol sulfateester, alkylsulfonic acid, alkyl allyl sulfonic acid, quaternaryammonium salt, oxyalkyl amine, fatty acid ester, polyalkylene oxidecompounds, anhydrosorbitol compounds, etc. These dispersants may be usedeither singly or in combination of two or more species.

[0069] A.3. Carriers

[0070] As the carrier that can be used in the antimicrobial compositionsof this invention, one may cite any dispersant that does not adverselyaffect the active ingredients, for example, clays (for example, kaolin,bentonite, acid clay, etc.), talcs (for example, talc powder,agalmatolite powder, etc.), silicas (for example, diatomaceous earth,silicic acid anhydride, mica powder, etc.), alumina, sulfur powder,activated charcoal, etc. These carriers may be used either singly or incombination of two or more species.

[0071] A.4. Other Components

[0072] The antimicrobial compositions of this invention may also containother antimicrobial agents (for example, organic chlorine-basedbiocides, organic phosphorus-based biocides, organic iodine-basedbiocides, organic sulfur-based biocides, organic nitrogen-basedbiocides, organic nitrogen-sulfur-based biocides, benzimidazole-basedbiocides, phenol-based biocides, organic acid ester-based biocides,antibiotics, etc.), insecticides (for example, natural insecticides,carbamate-based insecticides, organic phosphor-based insecticides,etc.), adjuvants (for example, casein, gelatin, starch, alginic acid,agar, CMC, polyvinyl alcohol, vegetable oil, bentonite, cresol soap,etc.), degradation prevention agents, scents etc.

[0073] The antimicrobial compositions of the present invention mayoptionally further comprise quaternary ammonium salts such as quaternaryammonium salts of the trimethyl alkyl ammonium halide type, e.g.trimethyl decyl ammonium chloride, trimethyl dodecylammonium chloride,trimethyl tallow ammonium chloride, trimethyl oleyl ammonium chloride;or of the dimethyl alkyl benzyl ammonium type, e.g. dimethyl decylbenzyl ammonium chloride, dimethyldodecyl benzyl ammonium chloride,dimethyl hexadecylbenzyl ammonium chloride (commonly designated as“cetalkonium chloride”), dimethyl octadecyl benzyl ammonium chloride,dimethyl coco benzyl ammonium chloride, dimethyl tallow benzyl ammoniumchloride; and particularly the dimethyl C₈₋₁₈alkyl benzyl ammoniumchloride mixture which is commonly known as “benzalkonium chloride”;dimethyl dialkyl ammonium halides, e.g. dimethyl dioctyl ammoniumchloride, dimethyl didecyl ammonium chloride, dimethyl didodecylammonium chloride, dimethyl dicoco ammonium chloride, dimethyl ditallowammonium chloride, dimethyl octyl decyl ammonium chloride, dimethyldodecyl octyl ammonium chloride, dimethyl dihydrogenated tallow ammoniumchloride.

[0074] B. Target Organisms

[0075] The antimicrobial compositions of this invention are generallywidely effective against bacteria, fungi, yeast, algae, etc., and it hasan antimicrobial spectrum that is broader than that of antimicrobialcompositions obtained by prescribing3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide or any ofthe compounds (a)-(m) singly. The antimicrobial compositions areinhibiting the growth or killing against the following organisms;bacteria such as Bacillus, Staphylococcus, Enterobacter, Escherichia,Pseudomonas, etc., fungi such as Aspergillus, Aureobasidium, Chaetomium,Cladosporium, Gliocladium, Penicillium, Trichoderma, etc., yeasts suchas Candida, Rhodotorula, etc., and algae such as Chlorella,Trentepohlia, Nostoc, Phormidium, etc.

[0076] The antimicrobial compositions of this invention may be appliedto various industrial products and industrial raw materials. As suchvarious industrial products and industrial raw materials, one may citefiber, paint, adhesive, wood, leather, processed paper products,electronic components, wall materials, resin moldings, etc.

WORKING EXAMPLES

[0077] By the following working examples, we describe in greater detailthe antimicrobial effectiveness of the antimicrobial compositions ofthis invention. The term “MIC” as used in these working examples refersto the minimum inhibitory concentration (ppm) of the active ingredientin the antimicrobial compositions. More specifically, it refers to theminimum concentration of the mixture of3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m) in the antimicrobial compositions that is able toinhibit the growth of bacteria, fungi or algae.

[0078] Preparing Bacterial Suspensions for Inoculation

[0079] The bacterial suspensions for inoculation used in working example1 were prepared as follows. Two bacteria, Staphylococcus aureus IFO12732 and Escherichia coli IFO 3972, where inoculated respectively intotwo separate nutrient broth culture media, they were shake-cultured for4-6 hours at 30° C., and two bacterial suspensions for inoculation werethus prepared.

[0080] Preparing Spore Suspensions for Inoculation

[0081] The spore suspensions for inoculation used in working example 2were prepared as follows. Two fungi, Aspergillus niger IFO 6341 andPenicillium funiculosum IFO 6345, were cultured on two potato dextroseagar culture media not containing any biocides, and spores were formed.Next, said fungus spores were dispersed in disinfectant water to which0.005% lubricant had been added, and two spore suspensions forinoculation were thus prepared.

[0082] Preparing Algae Suspensions for Inoculation

[0083] The algae suspensions for inoculation used in working example 3were prepared as follows. Bold's Basal liquid culture medium (50 ml) wasinoculated with Chlorella pyrenoidosa NIES 226, it was shake-culturedfor 14 days at 25° C., and algae suspensions for inoculation was thusprepared.

Working Example 1

[0084] Antimicrobial compositions were prepared by adding3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m) to dimethyl sulfoxide in the weight ratios listed inTables 1 and 2 below. Next, test culture media were prepared by addingeach of the varying diluted aqueous solutions (0.2 ml) of theantimicrobial compositions to a nutrient broth culture medium (10 ml).Each of these test culture media was inoculated with the above bacterialsuspensions for inoculation (0.1 ml), and after culturing for 24 hoursat 30° C. Then, the presence or absence of bacteria growth was assessedby visually observing the turbidity of the culture medium. The minimumconcentration of mixture of3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m) that was able to inhibit the growth of bacteria in theculture medium was taken as the MIC. Tables 1 and 2 list the MIC, foreach bacterium, of the antimicrobial compositions of each weight ratio.TABLE 1 Minimum inhibitory concentration (ppm) against Staphylococcusaureus Components 1:0 3:1 1:1 1:3 0:1 A:a 4 4 4 4 20 A:b 4 4 4 4 20 A:c4 4 4 10 40 A:d 4 4 4 4 10 A:e 4 4 4 4 10 A:f 4 2 2 2 4

[0085] TABLE 2 Minimum inhibitory concentration (ppm) againstEscherichia coli Components 1:0 3:1 1:1 1:3 0:1 A:a 200 200 200 200 400A:b 200 200 200 400 1000 A:c 200 40 40 40 40 A:d 200 100 100 100 200 A:e200 100 100 100 200 A:f 200 20 10 10 10

Working Example 2

[0086] Antimicrobial compositions were prepared by adding3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m) to dimethyl sulfoxide in the weight ratios listed inTables 3 and 4 below. Next, test culture media were prepared by addingeach of the varying diluted aqueous solutions (0.3 ml) of theseantimicrobial compositions to a potato dextrose agar culture medium (15ml). Each of these test culture media was inoculated with the abovespore suspensions for inoculation (1 ml), and after culturing for 7 daysat 28° C. Then, the presence or absence of fungus growth on each culturemedium was observed visually. The minimum concentration of mixture of3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m) that was able to inhibit the growth of fungi on theculture medium was taken as the MIC. Tables 3 and 4 list the MIC, foreach fungus, of the antimicrobial composition of each weight ratio.TABLE 3 Minimum inhibitory concentration (ppm) against Aspergillus nigerComponents 1:0 3:1 1:1 1:3 0:1 A:a 10 2 1 1 1 A:b 10 2 1 1 1 A:c 10 4 44 10 A:d 10 10 10 20 400 A:e 10 10 10 2 400 A:f 10 4 4 4 10 A:h 10 2 1 11 A:i 10 1 0.4 0.4 0.4

[0087] TABLE 4 Minimum inhibitory concentration (ppm) againstPenicillium funiculosum Components 1:0 3:1 1:1 1:3 0:1 A:a 2 1 1 1 4 A:b2 1 1 1 4 A:c 2 1 1 1 1 A:d 2 1 1 1 1 A:e 2 1 1 1 2 A:f 2 1 1 1 1 A:h 21 1 1 1 A:i 2 0.4 0.2 0.2 0.2

Working Example 3

[0088] Antimicrobial compositions were prepared by adding3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m) to dimethyl sulfoxide in the weight ratios listed inTable 5 below. Next, test culture media were prepared by adding each ofthe varying diluted aqueous solutions (0.1 ml) of these antimicrobialcompositions to Bold's Basal agar culture medium (15 ml). Each of thesetest culture media was inoculated with the above algae suspensions forinoculation (1 ml), and after culturing for 14 days at 25° C. and 1500lux. Then, the presence or absence of algae growth on each culturemedium was observed visually. The minimum concentration of mixture of3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide andcompounds (a)-(m) that was able to inhibit the growth of algae on theculture medium was taken as the MIC. Table 5 lists the MIC, for algae,of the antimicrobial composition of each weight ratio. TABLE 5 Minimuminhibitory concentration (ppm) against Chlorella pyrenoidosa Components1:0 3:1 1:1 1:3 0:1 A:a 40 10 10 10 10 A:b 40 10 10 10 10 A:c 40 20 2020 20 A:d 40 40 40 40 100 A:e 40 20 20 20 40 A:f 40 20 10 10 10 A:g 400.2 0.1 0.1 0.1 A:h 40 20 20 20 40 A:i 40 20 20 20 20

[0089] The results shown in Tables 1-5 show that the antimicrobialcompositions of this invention, due to the synergistic effect of itsactive ingredients, have greater effectiveness and a broaderantimicrobial spectrum than previous antimicrobial compositions. Theyalso show that the concentration of an antimicrobial composition usedfor suppressing the same amount of bacteria, fungi, or algae is keptmuch lower than if an active ingredient is used singly.

EFFECTS OF THE INVENTION

[0090] This invention yields antimicrobial compositions comprising astheir active ingredients3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and one ormore selected from

[0091] (a) 1-[[(3-iodo-2-propynyl)oxy]methoxy]-4-methoxy benzene,

[0092] (b) 1-chloro-4-[[(3-iodo-2-propynyl)oxy]methoxy]benzene,

[0093] (c) Zinc 2-pyridine thiol-1-oxide,

[0094] (d) Copper 2-pyridine thiol-1-oxide,

[0095] (e) 2-pyridine thiol-1-oxide sodium salt,

[0096] (f) 2,2-dithio-bis(pyridine-1-oxide),

[0097] (g) 2-methylthio-4-t-butyl amino-6-cyclopropyl amino-s-triazine(irgarol),

[0098] (h) 3-iodo-2-propynyl butylcarbamate (IPBC),

[0099] (i) 2-(n-octyl)-3(2H)-isothiazolone (OIT), or

[0100] (j) 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone (DCOIT)

[0101] (k) 2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile(chlorothalonil)

[0102] (l)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenyl-methanesulfenamide(dichlofluanid)

[0103] (m)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)-methanesulfenamide(tolylfluanid).

[0104] Combining these active ingredients produces a synergistic effectof these components and provides antimicrobial compositions that arehighly safe, are high effective, and have a broad antimicrobialspectrum. Furthermore, because the concentration of the activeingredients contained in the antimicrobial compositions of thisinvention is kept low, it can be prepared at very low cost and haslittle effect on the environment. The antimicrobial compositions of thisinvention are effective for antibacterial, antifungal and antialgalpurposes on various industrial products and industrial raw materials.

1. An antimicrobial composition comprising3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and one ormore of the following compounds (a)1-[[(3-iodo-2-propynyl)oxy]methoxy]-4-methoxy benzene, (b)1-chloro-4-[[(3-iodo-2-propynyl)oxy]methoxy]benzene, (c) zinc 2-pyridinethiol-1-oxide, (d) copper 2-pyridine thiol-1-oxide, (e) 2-pyridinethiol-1-oxide sodium salt, (f) 2,2-dithio-bis(pyridine-1-oxide), (g)2-methylthio-4-t-butyl amino-6-cyclopropyl amino-s-triazine, (h)3-iodo-2-propynyl butylcarbamate, (i) 2-(n-octyl)-3(2H)-isothiazolone,(j) 4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone, (k)2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile, (l)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenyl-methanesulfenamide,or (m)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)-methanesulfenamide.2. An antimicrobial composition as claimed in claim 1 comprising3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and one ormore of the following compounds (a)1-[[(3-iodo-2-propynyl)oxy]methoxy]-4-methoxy benzene, (b)1-chloro-4-[[(3-iodo-2-propynyl)oxy]methoxy]benzene, (c) zinc 2-pyridinethiol-1-oxide, (d) copper 2-pyridine thiol-1-oxide, (e) 2-pyridinethiol-1-oxide sodium salt, (f) 2,2-dithio-bis(pyridine-1-oxide), (g)2-methylthio-4-t-butyl amino-6-cyclopropyl amino-s-triazine, (h)3-iodo-2-propynyl butylcarbamate, or (i)2-(n-octyl)-3(2H)-isothiazolone, (j)4,5-dichloro-2-(n-octyl)-3(2H)-isothiazolone, (k)2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile, (l)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenyl-methanesulfenamide,or (m)1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)-methanesulfenamide,in quantities producing a mutual synergistic antimicrobial effect.
 3. Acomposition according to any of claims 1 or 2 wherein the weight ratioof 3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and thecompounds (a)-(m) is in the range 20:1 to 1:20.
 4. A compositionaccording to claim 3 wherein the weight ratio of3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and thecompounds (a)-(m) is in the range 5:1 to 1:5.
 5. A composition accordingclaim 4 wherein the weight ratio of3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and thecompounds (a)-(m) is in the range 3:1 to 1:3.
 6. A composition accordingto any of claims 1 or 2 wherein the total content of3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and thecompounds (a)-(m) is in the range of 0.1% by weight to 95%.
 7. Acomposition according to claim 6 wherein the total content of3-benzo[b]thiene-2-yl-5,6-dihydro-1,4,2-oxathiazine-4-oxide and thecompounds (a)-(m) is in the range of 0.2% by weight to 60% by weight. 8.Use of a composition as claimed in any of claims 1 to 7 to protectmaterials against bacteria, fungi, yeast and algae.
 9. A method ofprotecting materials against bacteria, fungi, yeast, and algae, whereinthe said method comprises administration or application of a compositionaccording to any of claims 1 to
 7. 10. A process for preparing acomposition as claimed in any of claims 1 to 7, characterized in thatthe active ingredients are intimately mixed with each other.